JPH0410501B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a resin composite comprising a styrenic thermoplastic resin and an unsaturated polyester resin and/or a vinyl ester resin.

Styrenic thermoplastic resins, such as polystyrene resin, acrylonitrile-styrene resin, ABS
Resins have excellent cost/performance and are used in various fields. However, since it is thermoplastic, it is susceptible to thermal deformation, creep fracture, etc., and foamed molded products have problems with strength, surface hardness, etc., and their uses are limited.

Conventionally, various attempts have been made to overcome the above-mentioned drawbacks, but the current situation is that nothing satisfactory has been achieved. For example, the surface of a styrenic thermoplastic resin molded product is coated with unsaturated polyester resin or vinyl ester resin to improve its solvent resistance and thermal properties, and fibrous reinforcing materials are also used in conjunction with the coating. One example is an attempt to improve mechanical properties by using so-called FRP. However, when using this method, if an unsaturated polyester resin or vinyl ester resin is tried to be cured by contact with a styrene thermoplastic resin, the surface of the thermoplastic resin or the entire molded product will be significantly eroded before the resin is cured. is extremely difficult to achieve.

Therefore, the present inventor completed the present invention as a result of intensive research to overcome the drawbacks of the conventional methods and to enable a resin composite of a styrene thermoplastic resin and an unsaturated polyester resin and/or a vinyl ester resin. I let him do it.

That is, the present invention applies a primer () shown below to the surface of a styrenic thermoplastic resin molded article () and cures it, and then coats the surface with an unsaturated polyester resin (-1) and/or a vinyl ester resin. A method for producing a resin composite, which comprises coating or laminating (-2) together with a filler or a fibrous reinforcing material if necessary, and curing the mixture.

A primer () comprising a compound (A) represented by the general formula (a), an unsaturated polyester (B), and optionally a polymerizable monomer (C) other than the compound (A).

General formula (a) [However, m and n are each independent integers of 1 to 5 and satisfy the formula m-n≧0, and R is -H
or _-CH3 , and X is a polyhydric alcohol with at least 3 carbon atoms and a valence of 3 or more, or a polyhydric alcohol with a valence of 4 or more and a valence of 4 or more and at least one ether bond, and a hydroxyl group Represents an m+1-valent organic group having a structure excluding. ].

In this specification, (meth)acrylate means acrylate and/or methacrylate, and (meth)acrylic acid means acrylic acid and/or methacrylic acid.

The styrenic thermoplastic resin molded product () refers to a molded product of styrene polymer or styrene copolymer. For example, polystyrene resin, acrylonitrile-butadiene-styrene resin (ABS resin),
Molded products such as acrylonitrile-styrene resin (AS resin), acrylonitrile-acrylate-styrene resin (AAS resin), and methyl methacrylate-butadiene-styrene resin (MBS resin) can be mentioned. There are no particular restrictions on the shape of the molded product, such as flat plate, sheet, grout, etc.
There are molded products with specific shapes, foam molded products, etc. Among these styrene-based thermoplastic resin molded products, especially when polystyrene resin and ABS resin are used,
Although the effects of the present invention are greater and more preferable, the effects of the present invention are particularly preferred in the case of foamed molded articles made of polystyrene resin, since the effects of the present invention are most effectively exhibited.

Primer () contains compound (A), as described above.
It consists of an unsaturated polyester (B) and an optional polymerizable monomer (C). Compound (A) is
Polyfunctional (meth)acrylates having two or more acryloyloxy groups and/or methacryloyloxy groups in the molecule represented by general formula (a), and as such compounds (A), diethylene glycol di(meth)acrylate , dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, glycerin di(meth)acrylate, ) acrylate, glycerin tri(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di( Examples include meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and one or more of these may be used. Among these (meth)acrylates, those that are liquid at room temperature are preferred.

The unsaturated polyester (B) contains α,β-unsaturated carboxylic acid ester groups and has a molecular weight of about 300 to
5000 polyester. The content of the α,β unsaturated carboxylic acid ester groups is at least 3 mol %, preferably 7 mol % or more, based on the total ester groups in the unsaturated polyester (B). Such unsaturated polyester (B) can be easily produced according to conventionally known methods. For example, an α,β-unsaturated dicarboxylic acid and/or its anhydride is essential as the acid component, a saturated dicarboxylic acid and/or its anhydride is used as necessary, and a glycol and/or an alkylene oxide which is a glycol precursor is used as the alcohol component. A method in which a monocarboxylic acid or a trifunctional A method using the above polycarboxylic acid as a modifier; the terminal carboxyl group of the unsaturated polyester obtained in this way and an epoxy compound containing an α,β unsaturated carboxylic acid ester group represented by glycidyl methacrylate are Reaction method: saturated dicarboxylic acid and/or its anhydride as an acid component and, if necessary, a modifier such as a monocarboxylic acid, to obtain a terminal carboxylic acid type saturated polyester and α, β typified by glycidyl methacrylate.
- A method of reacting with an epoxy compound containing an unsaturated carboxylic acid ester group.

Acid components used in producing the unsaturated polyester (B) include α,β-unsaturated dicarboxylic acids such as maleic anhydride, fumaric acid, and itaconic acid; phthalic anhydride, terephthalic acid, isophthalic acid, and succinic acid. , saturated dicarboxylic acids such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 3,6-endomethylenehexachlorophthalic anhydride, and adipic acid. Alcohol components include ethylene glycol, propylene glycol, neopentyl glycol,
Alkylene glycols such as 1,6-hexanediol; polyalkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol; ethylene oxide, propylene oxide, epichlorohydrin, allyl glycidyl ether, etc. Alkylene oxides: addition reaction products of polyvalent phenols such as bisphenol A and alkylene oxides, allyl ether groups such as trimethylolpropane monoallyl ether, pentaerythritol diallyl ether, glycerin monoallyl ether, trimethylolethane monoallyl ether, etc. Containing glycols and the like can be mentioned. In addition, as a denaturing agent, hexyl alcohol,
Tetrahydrofurfuryl alcohol, 8(9)-hydroxy-tricyclo[ ^{5,2,1,02,6 ]} deca-
Monohydric alcohols such as 3-ene, trimethylolpropane diallyl ether, glycerin diallyl ether, allyl cellosolve, addition reaction products of allyl alcohol and alkylene oxide; glycerin, trimethylolpropane, pentaerythritol monoallyl ether, pentaerythritol, Trivalent or higher polyhydric alcohols such as tris(2-hydroxyethyl) cyanurate can be mentioned.

Unsaturated polyester (B) obtained in this way
Among them, tetrahydrophthalic acid, methyltetrahydrophthalic acid, 3,6-endomethylenetetrahydrophthalic acid, or anhydride thereof is used in a proportion of at least 10 mol%, preferably 20 mol% or more of the acid component, and the alcohol component an unsaturated polyester (B-1) derived using polyalkylene glycols in a proportion of at least 20 mol%, preferably 30 mol% or more, and an allyl ether group content of at least 0.1 equivalent/1000 g,
Allyl ether group-containing glycols, allyl glycidyl ether, trimethylolpropane diallyl ether, glycerin diallyl ether, allyl cellosolve, addition reaction products of allyl alcohol and alkylene oxide, pentaerythritol mono, preferably in a ratio of 0.3 equivalent/1000 g. The unsaturated polyester (B-2) derived using allyl ether or the like is preferable because it quickly develops adhesive strength with the styrene thermoplastic resin molded product (). Among them, polyalkylene glycols include glycols represented by the general formula H(-OCH ₂ CH ₂ ) _-l OH (where l represents an integer from 2 to 20) such as diethylene glycol, triethylene glycol, and polyethylene glycol. The unsaturated polyester (B-1) derived using the above is particularly preferred, and among these, those derived using glycidyl methacrylate as a part of the glycol component and/or the terminal modifier are more preferred.

Polymerizable monomers (C) other than compound (A) that may be used as necessary include styrene, chlorostyrene, vinyltoluene, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and octyl (meth)acrylate. , ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc., and one or two of these compounds The above can be selected and used as appropriate.

The primer () is a compound (A) as described above,
It is composed of an unsaturated polyester (B) and a polymerizable monomer (C) if necessary, and the weight ratio of the compound (A) to the unsaturated polyester (B) is 9/1 to 1/9. The polymerizable monomer (C) is used in an amount of 40% or less of the total weight of the compound (A) and the unsaturated polyester (B). If the proportion of compound (A) and unsaturated polyester (B) used is out of the above range, the curing rate at room temperature will be slow or the viscosity of the primer () will increase too much, which is not preferable.
The proportion of the polymerizable monomer (C) used is as described above. However, for example, when the amount of styrene used is 30% of the total weight of compound (A) and unsaturated polyester (B), when the polystyrene foam molded product and the primer ( It is undesirable because it corrodes the surface of the surface. That is, an appropriate amount to be used is determined within the above range depending on the type of polymerizable monomer (C) and the type and shape of the styrenic thermoplastic resin molded article ().

In preparing the primer (), various additives known in the unsaturated polyester resin industry,
For example, gelling regulators, storage stabilizers, curing accelerators,
Antifoaming agents, leveling agents, surface drying agents, ultraviolet absorbers, thixotropic agents, etc. can be effectively used.

The primer () obtained in this way is
Curing can be carried out using polymerization initiators commonly used in the art. As a polymerization initiator, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide,
Peroxides such as t-butyl perbenzoate and methyl isobutyl ketone peroxide can be used, and if necessary, a curing accelerator can be used together with the polymerization initiator. Organic amines such as aliphatic amines and aromatic amines as curing accelerators; cobalt naphthenate, cobalt octenoate,
Examples include organic metal salts and chelates such as vanadium acetonate and cobalt acetonate. Furthermore, it can be cured by using a photosensitizer and ultraviolet rays, or by irradiation with electron beams or the like.

One method of using the primer () is to coat the surface of the styrene thermoplastic resin molded product () with a brush, roll coater, flow coater, spray, depping, or other known method to a thickness of at least 0.01 mm, preferably 0.04 mm. There is a method of applying and curing the material as described above. Also at this time,
If necessary, fillers, coloring agents, reinforcing materials, patterning materials such as printing paper, etc. known in the art may also be used.

The primer () applied to the surface of the styrenic thermoplastic resin molded product () in this way is
It is cured at room temperature or under mild heating to the extent that the molded article does not deform.

The degree of curing at that time does not necessarily mean that the primer () is completely cured, and when applying and curing unsaturated polyester resin (-1) or vinyl ester resin (-2) on the surface By the time the resin is cured, it has hardened to a degree that can prevent the styrenic thermoplastic resin molded product () from being eroded by the main reactive monomers in it, such as styrene and aromatic vinyl compounds such as vinyltoluene. All you have to do is For example, if the amount of primer () applied is large or the subsequent resin cures quickly, the degree of curing of primer () may be relatively low; conversely, if the amount of primer () applied is small or the subsequent resin If the curing of the primer () is slow, it is necessary to increase the degree of curing of the primer (). Therefore, the minimum required degree of curing of the primer () will vary depending on each case, but it can be easily determined by carrying out simple experiments in each case, and the present invention It is not influenced by differences.

As the unsaturated polyester resin (-1) and/or vinyl ester resin (-2), conventionally known ones can be freely used, but among them, styrene and vinyl toluene are used as the main component of the polymerizable monomer. When using a resin containing an aromatic vinyl compound such as, the effects of the present invention are most effectively exhibited.

Examples of unsaturated polyester resins (-1) include "Polyester Resin" by Eiichiro Takiyama.
(February 28, 1970, published by Nikkan Kogyo Shimbun) 2. Those listed in the chemistry section of unsaturated polyester resins can be mentioned. As an example of vinyl ester resin (-2), for example, in Patent Publication No. 7791 of 1978, "epoxy ester resin"
"Reaction products of epoxy resins and polymerizable unsaturated carboxylic acids, or carboxylic acids and/or carboxylic acid anhydrides containing epoxy resins and polymerizable unsaturated carboxylic acids as main components" A thermosetting resin obtained by dissolving a reaction product of the above in a polymerizable unsaturated monomer.

When using the unsaturated polyester resin (-1) or the vinyl ester resin (-2), commercially available products can be effectively utilized according to methods conventionally known in the unsaturated polyester resin industry. For example, fillers, colorants, reinforcing materials, patterning materials such as printing paper, etc. may be used as necessary, and a curing agent may be used together with a curing accelerator as necessary, and the material may be coated or laminated and cured.

The resin composite obtained according to the method of the present invention is
A styrenic thermoplastic resin and a layer of unsaturated polyester resin and/or vinyl ester resin are firmly integrated via a primer (), and the thermal, mechanical, The chemical properties have been greatly improved, and the fields of application of the molded article can be greatly expanded.

Hereinafter, the present invention will be explained in more detail by giving examples. In addition, "parts" in the examples represent "parts by weight."

Example 1 An unsaturated polyester (polyester (1) ) was obtained. Next, 60 parts of polyester (1),
40 parts of trimethylolpropane triacrylate,
Uniformly dissolve 0.02 parts of hydroquinone, 0.05 parts of paraffin, and 10 parts of styrene, and
-1) was obtained.

A resin solution containing 100 parts of primer (-1), 1.0 part of cobalt octenoate (metal content: 8% by weight, the same applies hereinafter) and 1.5 parts of methyl ethyl ketone peroxide (oxide content: 55% by weight, the same applies hereinafter) was mixed 30 times. After coating the top surface of the expanded polystyrene foam plate to a coating thickness of approximately 500μ,
It was left at room temperature. Primer (-1) gelled 30 minutes after blending with methyl ethyl ketone peroxide, and after 5 hours of gelation, the interior of primer (-1) was hardened although the surface was somewhat sticky.

Next, unsaturated polyester resin (manufactured by Nippon Shokubai Chemical Co., Ltd., Epolack G-753PTM) is applied to the top surface.
A resin solution containing 1.0 parts of methyl ethyl ketone peroxide in 100 parts and glass fiber (MC- manufactured by Nittobo Co., Ltd.)
450A), FRP was laminated and molded so that the weight ratio of resin liquid and glass fiber was approximately 70:30 and the thickness was 3 mm. After 5 hours, the FRP was substantially completely cured, yielding a resin composite firmly integrated with the polystyrene foam. Later, when this resin composite was cut and inspected, it was found that the polystyrene foam layer was not eroded at all.

Example 2 Maleic anhydride, tetrahydrophthalic anhydride and diethylene glycol were used in a molar ratio of 0.7:0.3:1.2 according to a conventional method to obtain an acid value of 23.
An unsaturated polyester (polyester (2)) was obtained. Next, 60 parts of polyester (2), 40 parts of trimethylolpropane triacrylate, and hydroquinone.
Primer (-2) was obtained by uniformly dissolving 0.02 parts and 5 parts of styrene.

A resin solution containing 100 parts of primer (-2), 1.0 part of cobalt octenoate, and 1.5 parts of methyl ethyl ketone peroxide was applied to the top surface of a 30 times expanded polystyrene foam plate to a coating thickness of approximately 200μ, and then heated at room temperature. I left it alone. Primer (-2) gelled approximately 42 minutes after blending with methyl ethyl ketone peroxide, and after 4 hours of gelation, it was uniformly hardened to the surface.

Next, FRP was laminated and molded on the upper surface in the same manner as in Example 1 to obtain a resin composite. When this resin composite was tested in the same manner as in Example 1, it was found that the polystyrene foam layer was not corroded at all.

Example 3 608 parts of tetrahydrophthalic anhydride and 318 parts of diethylene glycol were esterified according to a conventional method, and when the acid value reached 126, the reaction system was reduced to 110 parts.
Cool to 110°C, add 190 parts of styrene, 3 parts of triethylamine, 5 parts of hydroquinone and 280 parts of glycidyl methacrylate, and react at 110°C.
When the acid value reached 16, 770 parts of triethylene glycol dimethacrylate was added to obtain primer (-3).

A resin solution containing 100 parts of primer (-3), 2.0 parts of cobalt octenoate, and 1.0 parts of methyl ethyl ketone peroxide was applied onto the surface of a 20 mm thick 60x expanded polystyrene foam to a thickness of approx.
After coating to a thickness of 60μ, it was cured at room temperature for 3 hours. Next, FRP with a thickness of about 3 mm was laminated and molded on the surface in the same manner as in Example 1 to obtain a resin composite having a core of expanded polystyrene and a surface of FRP.

Example 4 392 parts of maleic anhydride and 228 parts of propylene glycol were esterified in a conventional manner, and when the acid value reached 191, the reaction temperature was raised to 130°C.
Add 228 parts of allyl glycidyl ether, 3.7 parts of hydroquinone and 1.5 parts of triethylamine.
The reaction was carried out at 130°C, and when the acid value reached 21, 185 parts of tetraethylene glycol diacrylate and 100 parts of styrene were added to prepare primer (-4).
I got it.

A resin solution containing 100 parts of primer (-4), 1.0 part of cobalt octenoate, and 1.0 part of methyl ethyl ketone peroxide was foamed 60 times to 600 x 300.
It was applied to the entire surface of a 10 mm x polystyrene foam to a coating thickness of about 100 μm, and cured at room temperature for 5 hours. Next, apply 100% vinyl ester resin (manufactured by Nippon Shokubai Chemical Co., Ltd., Epolack RF-1001) to the surface.
0.1 part paraffin, 0.1 part cobalt octenoate
FRP was laminated and molded in the same manner as in Example 1 using a resin solution containing 0.1 part of dimethylaniline and 1.5 parts of methyl ethyl ketone peroxide and glass fiber (MC-450A manufactured by Nittobo Co., Ltd.) to obtain a resin composite. I got it.

Example 5 In Example 3, tetrahydrophthalic anhydride
A primer (-5) having an acid value of 12 was obtained in the same manner as in Example 3, except that 304 parts of tetrahydrophthalic anhydride and 196 parts of maleic anhydride were used instead of 608 parts.

A resin liquid containing 100 parts of primer (-5), 2.0 parts of cobalt octenoate, and 1.0 parts of methyl ethyl ketone peroxide is foamed 30 times to a thickness of 30 mm.
The coating thickness on both sides of the polystyrene foam plate is approx.
After coating it to a thickness of 60μ and curing it at room temperature for 4 hours, coat it on both sides in the same manner as in Example 1.
By laminating and molding FRP, a resin composite with a sandwich structure consisting of FRP on both sides and polystyrene foam core was obtained.

Example 6 100 parts of the primer (-5) obtained in Example 5, 100 parts of calcium carbonate powder, and 2.0 parts of cobalt octenoate.
A composition containing 1.0 parts of methyl ethyl ketone peroxide and 1.0 parts of methyl ethyl ketone peroxide was applied to both sides of a 30 mm thick polystyrene foam plate with a thickness of approximately 500 μm.
After applying and curing at room temperature for 90 minutes,
Furthermore, FRP with a thickness of about 2.0 mm was laminated and molded on both sides in the same manner as in Example 1 to obtain a resin composite having a sandwich structure with FRP on both sides and polystyrene foam at the core.

Example 7 In Example 5, a 2 mm thick ABS resin flat plate (a molded product of Diapet ABS manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of the polystyrene foam flat plate, except that both sides were made of FRP. A resin composite with a sandwich structure with a core made of ABS resin was obtained.

Claims (1)

[Claims] 1. After coating the surface of a styrenic thermoplastic resin molded product () with the primer () shown below and curing it, the surface is further coated with unsaturated polyester resin (-1) and/or vinyl. A method for producing a resin composite, which comprises applying or laminating an ester resin (-2) together with a filler or a fibrous reinforcing material if necessary, and curing the resin composite. A primer () comprising a compound (A) represented by the general formula (a), an unsaturated polyester (B), and optionally a polymerizable monomer (C) other than the compound (A). General formula (a) [However, m and n are each independent integers of 1 to 5 and satisfy the formula m-n≧0, and R is -H
or _-CH3 , and X is a polyhydric alcohol with at least 3 carbon atoms and a valence of 3 or more, or a polyhydric alcohol with a valence of 4 or more and a valence of 4 or more and at least one ether bond, and a hydroxyl group Represents an m+1-valent organic group having a structure excluding. ]